EP0194591A2 - Procédé de préparation de 2-alkyl-cyclopentanones - Google Patents

Procédé de préparation de 2-alkyl-cyclopentanones Download PDF

Info

Publication number
EP0194591A2
EP0194591A2 EP86102996A EP86102996A EP0194591A2 EP 0194591 A2 EP0194591 A2 EP 0194591A2 EP 86102996 A EP86102996 A EP 86102996A EP 86102996 A EP86102996 A EP 86102996A EP 0194591 A2 EP0194591 A2 EP 0194591A2
Authority
EP
European Patent Office
Prior art keywords
hydrogen
cyclopentanone
catalyst
autoclave
general formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP86102996A
Other languages
German (de)
English (en)
Other versions
EP0194591B1 (fr
EP0194591A3 (en
Inventor
Walter Dr. Gramlich
Wolfgang Dr. Lengsfeld
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0194591A2 publication Critical patent/EP0194591A2/fr
Publication of EP0194591A3 publication Critical patent/EP0194591A3/de
Application granted granted Critical
Publication of EP0194591B1 publication Critical patent/EP0194591B1/fr
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/385—Saturated compounds containing a keto group being part of a ring
    • C07C49/395—Saturated compounds containing a keto group being part of a ring of a five-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/73—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with hydrogenation

Definitions

  • the present invention relates to a process for the preparation of cyclo-pentanones monoalkylated in the a-position which is significantly improved over the prior art.
  • alkylation of cyclopentanone with alkyl halides in the presence of bases is also known.
  • Gupta et. al cf. J. Indian Chem. Soc. 30 (1953), pages 23 to 25
  • alkylation of cyclopentanone with alkyl bromides e.g. Heptyl bromide
  • the 2-heptyl-cyclopentanone obtained could not be isolated as a result of numerous by-products.
  • the enamine obtained was refluxed in a second stage with an aldehyde for 12 hours in benzene as solvent under reflux.
  • the cooled solution was then acidified with dilute hydrochloric acid, stirred for 1 hour, extracted with benzene, the benzene extract washed with water, all of the benzene distilled off and the residue fractionated.
  • the alkylidene cyclopentanones were thus obtained in a yield of 40 to 75%.
  • akylidene compounds were then hydrogenated to the a-alkyl-cyclopentanones in the presence of a hydrogenation catalyst.
  • the disadvantage of this process is that it consists of three sometimes very lengthy process steps and that it only gives medium yields.
  • a production process with the use of amines is not very recommendable, since the alkylated cyclopentanones are largely used as fragrances and because the olfactory properties are therefore subject to the highest demands.
  • Components on the one hand contain an oxide or a phosphate of magnesium, aluminum, titanium, zinc or one of the rare earth metals and on the other hand contain a noble metal from group VIII of the periodic table, preferably palladium.
  • the process is particularly advantageous if the reaction is carried out under a hydrogen pressure of from 1 to about 300, preferably from 10 to about 100, in particular from 10 to 50, bar.
  • the process is very advantageous if the reaction is carried out in the absence of substantial amounts of a solvent, since the space-time yields are thereby substantially improved and the workup is facilitated without loss of yield.
  • the process according to the invention is generally carried out in an autoclave in such a way that all components, i.e. submit the cyclopentanone of the formula II or the corresponding cyclopentenone, the aldehyde of the formula III and the heterogeneous catalyst, close the autoclave and then flush first with nitrogen and then with hydrogen. The mixture is then heated to the reaction temperature while injecting hydrogen.
  • the autoclave After the reaction is complete, the autoclave is cooled, let down and the discharge is sucked out through a filter and thus separated from the catalyst.
  • the catalyst can be flushed back into the autoclave with new starting materials for the next batch using the same filters.
  • the catalyst can also be left in the autoclave using an appropriately long riser pipe with a frit to discharge the liquid phase.
  • the catalyst can be used several times.
  • the liquid reactor discharge obtained only needs to be distilled off. If necessary, the water of reaction formed can be separated off as the lower phase before the distillation.
  • the catalyst can also be used as a carrier catalyst, e.g. in the form of spheres or strands, install them firmly in a reactor column and continuously pass the mixture of cyclopentanone or pentenone and aldehyde over the catalyst under the conditions according to the invention.
  • the catalyst according to the invention is, in principle, a catalyst system consisting of two components.
  • the oxides or phosphates of magnesium, aluminum, titanium, zinc and one of the rare earths, such as praseodymium oxide (Pr 4 0 6 ), are suitable for this step.
  • the oxides of aluminum have proven to be particularly suitable and advantageous.
  • the catalyst contains a noble metal from group VIII of the periodic table, in particular palladium.
  • the other precious metals - platinum, ruthenium, rhodium, iridium and osmium - are also suitable, but are generally less suitable for economic reasons.
  • the catalyst can be present both in the form of a mixture of the condensation catalyst, such as A1 2 0 3 , and the hydrogenation catalyst, such as palladium on activated carbon, and in the form of a uniform catalyst, for example one containing palladium on A1 2 0 3 .
  • the condensation catalyst such as A1 2 0 3
  • the hydrogenation catalyst such as palladium on activated carbon
  • a uniform catalyst for example one containing palladium on A1 2 0 3 .
  • the only thing that is essential is the simultaneous presence of both catalyst components.
  • the noble metal content is generally between 0.1 and 5% by weight. Preference is given to catalysts which contain palladium as noble metal with a content of 0.5 to 1 /, based on the amount of catalyst used.
  • Suspension catalysts are used for discontinuous operation. If the reaction is carried out continuously in a reactor column, preference is given to using supported catalysts on which the noble metal, e.g. the palladium is applied. You can use the carrier material. which consists of the condensation component, impregnated with an aqueous solution containing a palladium salt such as palladium nitrate.
  • the palladium metal then forms automatically under the hydrogenating conditions, but the catalyst can also be subjected to a separate hydrogenation for this purpose.
  • the catalyst used in the continuous mode of operation can be used in the form of tablets, granules, spheres or extrudates; in the case of a batchwise mode of operation, the powder form is often used.
  • the corresponding cyclopentenones such as 3-methyl-cyclopent-2-enone
  • the double bond present also being hydrogenated under the reaction conditions, such as the double bond formed in the condensation.
  • the double bond can be in any position; in this case R 2 or R 2 and R 4 or R 4 and R 6 represent the proportion of a double bond.
  • the straight-chain unsubstituted aldehydes such as propanal, butanal, pentanal, hexanal, heptanal, octanal, nonanal, decanal, undecanal and dodecanal, as well as various branched and substituted ones, for example the 2-methyl-propanal, 2- Methyl-butanal, 2-methyl-pentanal, 2-methyl-hexanal, 2-methyl-heptanal, 2-methyl-octanal, 2-methyl-nonanal, 2-methyl decanal, 2-methyl-undecanal, 3-methyl- Use butanal and 3-methyl-pentanal.
  • aldehydes such as propanal, butanal, pentanal, hexanal, heptanal, octanal, nonanal, decanal, undecanal and dodecanal, as well as various branched and substituted ones, for example the 2-methyl-propanal, 2- Methyl
  • the molar ratio of cyclopentanone to aldehyde can be 1 to 1, but an excess of the cheaper reactant is preferably used, as a result of which the selectivity, based on the more expensive reactant, can be increased considerably.
  • a solvent such as methanol, ethanol or propanol can also be used.
  • the reaction temperature for the process according to the invention depends on the starting components and the type and amount of the catalyst used. It can fluctuate between 80 and 280 ° C; when using large amounts of catalyst, it can also be below 80 ° C.
  • the preferred temperature range for an economical process is between 100 and 200 ° C.
  • the amount of catalyst used varies depending on the reactivity of aldehyde and cyclopentanone derivative. Amounts of 3 to 8% by weight, based on the sum of the starting compounds, are preferably used.
  • the hydrogen pressure can also be varied within wide limits and depends on the content of the noble metal used.
  • a catalyst which is frequently used and which contains 0.5% by weight of palladium on aluminum oxide see Example 1
  • hydrogen pressures between 40 and 50 bar are sufficient.
  • a catalyst with a higher palladium content or when using larger amounts of the above 0.5 1 Pd / A1 2 0 3 catalyst lower hydrogen pressures are sufficient.
  • unsubstituted cyclopentanones or the corresponding cyclopentenones with many aliphatic aldehydes in the ⁇ -position to the keto group can be converted in a simple one-step reaction with virtually complete conversion in high selectivity to the desired ⁇ -monoalkylated cyclopentanones.
  • the process according to the invention is not only distinguished by better yields and better space / time yields, but also by its environmental friendliness, since no auxiliary bases or salts are used, but only in the presence of a heterogeneous catalyst, and therefore no saline waste water is obtained.
  • a technically particularly important product of the new process according to the invention is 2-heptyl-cyclopentanone, which is an important jasmine fragrance.
  • 2-heptyl-cyclopentanone which is an important jasmine fragrance.
  • cyclopentanones are also suitable as fragrances (cf. Perfumer and Flavorist 8 (1983), April / May issue, pages 68 to 74).
  • a mixture of 1000 ml (930 g; 11 mol) of cyclopentanone, 500 ml (425 g, 3.7 mol) of n-heptanal and 70 g of a powdery catalyst containing 0.5% by weight of palladium on aluminum oxide was placed in an autoclave. After flushing with nitrogen and hydrogen, a hydrogen pressure of 10 bar was applied at 25 ° C. and then heated to 110 ° C. for 3 hours (h) at a hydrogen pressure of 35 bar and finally at a pressure of 50 bar to 160 ° C., for which purpose about 10 hours were required. After the catalyst had been separated off, the reactor discharge was fractionated directly.
  • Example 1 Analogously to Example 1, a mixture of 1008 g (12 mol) of cyclopentanone, 800 g (8 mol) of n-hexanal and 80 g of a 0.5 wt 70 bar hydrogen pressure hydrogenated to constant pressure (approx. 15 h). After the catalyst had been separated off, the reactor discharge was distilled directly. 294 g (3.5 mol) of cyclopentanone were recovered as fraction 1. The main fraction obtained 1103 g of pure 2-hexyl-cyclopentanone (bp. 84 ° C / 0.35 mbar), which corresponds to a selectivity of 82 Z based on n-hexanal. As in Example 1, the molar ratio of cyclopentanone to hexanal was increased to 3: 1. the selectivity rose to over 90% as in the case of 2-heptyl-cyclopentanone.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP86102996A 1985-03-09 1986-03-06 Procédé de préparation de 2-alkyl-cyclopentanones Expired EP0194591B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853508420 DE3508420A1 (de) 1985-03-09 1985-03-09 Verfahren zur herstellung von 2-alkyl-cyclopentanonen
DE3508420 1985-03-09

Publications (3)

Publication Number Publication Date
EP0194591A2 true EP0194591A2 (fr) 1986-09-17
EP0194591A3 EP0194591A3 (en) 1986-12-30
EP0194591B1 EP0194591B1 (fr) 1988-08-24

Family

ID=6264695

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86102996A Expired EP0194591B1 (fr) 1985-03-09 1986-03-06 Procédé de préparation de 2-alkyl-cyclopentanones

Country Status (5)

Country Link
US (1) US5081309A (fr)
EP (1) EP0194591B1 (fr)
JP (1) JPH0627091B2 (fr)
DE (2) DE3508420A1 (fr)
ES (1) ES8706104A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0654460A1 (fr) * 1993-11-22 1995-05-24 Rhone-Poulenc Chimie Procédé de C-alkylation d'un compose cétonique

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3707209A1 (de) * 1987-03-06 1988-09-15 Henkel Kgaa 2-alkyliden-3,3,5(3,5,5)-trimethylcyclopentanone als riechstoffe
DE3837452A1 (de) * 1988-11-04 1990-05-10 Huels Chemische Werke Ag Verfahren zur herstellung von 2-methyl-5-n-alkylcyclopentanonen
CN103044374B (zh) * 2012-12-26 2014-10-29 淮安万邦香料工业有限公司 一种δ-十二内酯的合成方法
CN114075101A (zh) * 2020-08-20 2022-02-22 中国科学院大连化学物理研究所 一种2-烷基环己酮类化合物的制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2056450A5 (fr) * 1969-07-25 1971-05-14 Vyskumny Ustav Pre Petro
US3829495A (en) * 1969-05-14 1974-08-13 Tokuyama Soda Kk Method of producing dimerized saturated ketones
US4146581A (en) * 1976-04-08 1979-03-27 Basf Aktiengesellschaft Manufacture of higher ketones
EP0013385A1 (fr) * 1979-01-10 1980-07-23 BASF Aktiengesellschaft Procédé pour la préparation de composés carbonylés aliphatiques
EP0028703A1 (fr) * 1979-10-12 1981-05-20 BASF Aktiengesellschaft Procédé de préparation de composés carbonyliques alpha-substitués par un groupe méthyle
EP0100019A1 (fr) * 1982-07-22 1984-02-08 BASF Aktiengesellschaft Procédé pour la préparation de composés alpha-substitués bêta-dicarbonylés ou bêta-cyanocarbonylés et de bêta-dinitriles alpha-substitués
EP0127835A1 (fr) * 1983-05-28 1984-12-12 BASF Aktiengesellschaft Procédé de production de cétones

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE633595C (de) * 1933-10-17 1936-07-31 Givaudan & Cie Sa Verfahren zur Herstellung von Kondensationsprodukten der Cyclopentanone mit Aldehyden
US2288308A (en) * 1941-04-07 1942-06-30 Ivan A Williams Punch and die
US3701798A (en) * 1965-12-03 1972-10-31 Eastman Kodak Co Synthesis of unsaturated compounds
DE2525506C2 (de) * 1975-06-07 1983-09-15 Basf Ag, 6700 Ludwigshafen Verfahren zur Herstellung eines Nickel und/oder Kobalt und Zinkoxid enthaltenden Katalysators
DE2625541A1 (de) * 1976-06-05 1977-12-22 Basf Ag Verfahren zur herstellung einer zink und nickel oder kobalt enthaltenden kontaktmasse
JPS5925770B2 (ja) * 1979-06-13 1984-06-21 三菱瓦斯化学株式会社 メチルイソブチルケトンの製造法
US4270006A (en) * 1979-12-27 1981-05-26 Basf Aktiengesellschaft Preparation of aliphatic carbonyl compounds

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3829495A (en) * 1969-05-14 1974-08-13 Tokuyama Soda Kk Method of producing dimerized saturated ketones
FR2056450A5 (fr) * 1969-07-25 1971-05-14 Vyskumny Ustav Pre Petro
US4146581A (en) * 1976-04-08 1979-03-27 Basf Aktiengesellschaft Manufacture of higher ketones
EP0013385A1 (fr) * 1979-01-10 1980-07-23 BASF Aktiengesellschaft Procédé pour la préparation de composés carbonylés aliphatiques
EP0028703A1 (fr) * 1979-10-12 1981-05-20 BASF Aktiengesellschaft Procédé de préparation de composés carbonyliques alpha-substitués par un groupe méthyle
EP0100019A1 (fr) * 1982-07-22 1984-02-08 BASF Aktiengesellschaft Procédé pour la préparation de composés alpha-substitués bêta-dicarbonylés ou bêta-cyanocarbonylés et de bêta-dinitriles alpha-substitués
EP0127835A1 (fr) * 1983-05-28 1984-12-12 BASF Aktiengesellschaft Procédé de production de cétones

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0654460A1 (fr) * 1993-11-22 1995-05-24 Rhone-Poulenc Chimie Procédé de C-alkylation d'un compose cétonique
FR2712885A1 (fr) * 1993-11-22 1995-06-02 Rhone Poulenc Chimie Procédé de C-alkylation d'une cétone cyclique.
US5618982A (en) * 1993-11-22 1997-04-08 Rhone-Poulenc Chimie Catalytic C-alkylation of ketones

Also Published As

Publication number Publication date
JPH0627091B2 (ja) 1994-04-13
DE3660590D1 (en) 1988-09-29
EP0194591B1 (fr) 1988-08-24
US5081309A (en) 1992-01-14
DE3508420A1 (de) 1986-09-11
EP0194591A3 (en) 1986-12-30
ES8706104A1 (es) 1987-06-01
ES552759A0 (es) 1987-06-01
JPS61218548A (ja) 1986-09-29

Similar Documents

Publication Publication Date Title
EP2625158B1 (fr) Procédé de production de cétones, en particulier de cétones macrocycliques
DE1793801B1 (de) Verfahren zur herstellung von makrocyclischen verbindungen
EP0037584B1 (fr) 2.4-Dialcoyl-2.6-heptadiénals et -heptadiénols, procédé pour leur préparation et leur utilisation à titre d'ingrédients parfumants et aromatisants
EP0400509B1 (fr) Procédé de préparation de la muscone, produits intermédiaires pour ce procédé et leur préparation
CH617168A5 (fr)
EP0194591B1 (fr) Procédé de préparation de 2-alkyl-cyclopentanones
DE1237567B (de) Verfahren zur Herstellung von delta 5-6-Methylsteroiden
EP0100019B1 (fr) Procédé pour la préparation de composés alpha-substitués bêta-dicarbonylés ou bêta-cyanocarbonylés et de bêta-dinitriles alpha-substitués
EP0038480B1 (fr) Procédé de préparation de 1-(4-hydroxyphényl)-3-butanone et produits intermédiaires de ce procédé
DE3027269A1 (de) 3,6-dimethyl-3-hydroxy-1-octine und -1-octene sowie derivate davon und ihre verwendung als riechstoffe und verfahren zur herstellung von 3,6-dimethyl-3-hydroxy-octan
EP0017893B1 (fr) Procédé de préparation d'aralkylamines hétérocycliques tertiaires
EP0038471B1 (fr) Cétones bêta-gamma non saturés et diénones isoprénoiques, procédé pour leur préparation et leur utilisation à titre de parfumants et aromatisants
EP0509273B1 (fr) 2,5-Bis-(1',1'-dialkoxy-2'-propyl)-2,5-dihydrofurannes, procédé pour leur préparation, et leur utilisation dans la préparation de caroténoîdes
EP0075237B1 (fr) Procédé de préparation de dérivés des 1-formyl-2,6,6-triméthyl-cyclohex-1-ènes
DE2314697C3 (de) 1 -Amino^-hydroxy-SJ-dimethyloctane und Verfahren zu deren Herstellung
DE2640026C2 (de) Verfahren zur Herstellung von 6,10,14-Trimethylpentadecan-2-on
EP0358088B1 (fr) Procédé de préparation des 3-aryl-isobutanols
EP0097874B1 (fr) Procédé de préparation de 6-exo-alcanoyl-1,3,3-triméthyl-bicyclo(2.2.2.)octan-2-ones
DE3112056A1 (de) Verbessertes verfahren zur herstellung von cyclohexan-1,3-dionen sowie einige neue bicyclische cyclohexan-1,3-dione
EP0436860A1 (fr) ProcédÀ© pour la préparation de l'acide 2-(4-chlorophényl)-3-méthyl-butanoique
EP0251115B1 (fr) Procédé pour la fabrication d'arylcétones bêta-halovinyles et bêta, bêta-dihaloéthyles
EP0075866B1 (fr) Ethers macrobicycliqués substitués, leur préparation et leur usage
EP0994096B1 (fr) Procédé de préparation d'esters d'acide 2-méthyl-1,3-dicarboxylique
EP0398099B1 (fr) Procédé pour la préparation de cyclopentanones
DE2150992C3 (de) Verfahren zur Herstellung von a, ß-ungesättigten Ketonen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): BE CH DE FR GB IT LI NL

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): BE CH DE FR GB IT LI NL

17P Request for examination filed

Effective date: 19870129

17Q First examination report despatched

Effective date: 19870721

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE CH DE FR GB IT LI NL

ITF It: translation for a ep patent filed
REF Corresponds to:

Ref document number: 3660590

Country of ref document: DE

Date of ref document: 19880929

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19980226

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19980303

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19980311

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19980312

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19980313

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19980320

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990306

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF THE APPLICANT RENOUNCES

Effective date: 19990316

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990331

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990331

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990331

BERE Be: lapsed

Owner name: BASF A.G.

Effective date: 19990331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19991001

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19990306

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19991130

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19991001

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050306